CN112547128B - Catalyst composition and preparation method of high-carbon aldehyde - Google Patents
Catalyst composition and preparation method of high-carbon aldehyde Download PDFInfo
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- CN112547128B CN112547128B CN201910919014.6A CN201910919014A CN112547128B CN 112547128 B CN112547128 B CN 112547128B CN 201910919014 A CN201910919014 A CN 201910919014A CN 112547128 B CN112547128 B CN 112547128B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
- B01J31/2471—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
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Abstract
The invention provides a catalyst composition, which comprises a rhodium catalyst precursor and a ligand, wherein the ligand is a ligand I shown in a formula (I) and/or a ligand II shown in a formula (II). When the catalyst composition provided by the invention is used for preparing high-carbon aldehyde by high-carbon olefin hydroformylation, the olefin isomerization degree in the high-carbon olefin hydroformylation reaction process can be reduced, the high-carbon aldehyde yield is improved, and the selectivity of linear aldehyde in the high-carbon aldehyde generated by the reaction is increased.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a catalyst composition and a preparation method of high-carbon aldehyde.
Background
Hydroformylation is an important route to aldehydes or alcohols. The hydroformylation process (also called oxo process) adopted in the current industrial production has been ten or more, and most industrial devices use aldehydes and alcohols as main products.
The high-carbon hydroformylation of high-carbon olefin is an industrial production technology with higher comprehensive economic indexes, but the production technology of aldehyde and alcohol mastered by China is still concentrated on products such as C4 alcohol, C8 alcohol and the like, and the high-carbon alcohol products with the increased demand year by year are still in a starting stage in China, and have no independent intellectual property high-carbon olefin hydroformylation technology.
The cobalt catalysis process still plays a role in the current high-carbon olefin hydroformylation, but the comprehensive economic and technical indexes of the cobalt catalysis process are far less than those of the rhodium catalysis process due to the factors of harsh reaction conditions, poor selectivity, more side reactions, high energy consumption, complex cobalt recovery process and the like. Thus, research on hydroformylation of high-carbon olefins using rhodium catalysts has been continued, mainly from two aspects: on one hand, starting from a homogeneous catalysis system, developing a new phosphine ligand rhodium catalyst, so that the rhodium catalyst has higher catalytic activity and better stability; on the other hand, the problem of water solubility of high-carbon olefin is solved from the two-phase catalytic system, and a new two-phase catalytic system is developed. The two-phase catalytic system has lower reactivity than the homogeneous catalytic system, and particularly for high-carbon olefins with low water solubility, the hydroformylation is difficult to carry out due to the limitation of mass transfer, so that the two-phase catalytic system has lower reactivity. Thus, for the hydroformylation of high olefins, homogeneous catalytic systems remain a major concern.
The homogeneous catalysis of high-carbon olefin hydroformylation technology is mainly focused on the development of catalysts, and the important points are various ligands such as monophosphites, monohydrocarbylphosphites, bisphosphites, dihydrocarbylphosphorus, bisphosphites amides and ionic ligands. The low reaction rate and serious isomerization of high-carbon olefin lead to the common problem that the conversion rate and selectivity cannot reach higher level at the same time.
Disclosure of Invention
In order to solve the technical problems, the invention provides a catalyst composition which can reduce the isomerization degree of olefin in the hydroformylation reaction process of high-carbon olefin, improve the yield of high-carbon aldehyde and increase the selectivity of linear aldehyde in high-carbon aldehyde generated by the reaction when being used in the hydroformylation of high-carbon olefin to prepare high-carbon aldehyde.
In a first aspect, the present invention provides a catalyst composition comprising a rhodium catalyst precursor and a ligand, said ligand being a ligand I of formula (I) and/or a ligand II of formula (II),
in formula (I), X is selected from the group consisting of C6-C28 organic divalent bridging arylene, optionally substituted with substituents selected from the group consisting of cyano, nitro, halogen, C1-C6 alkyl, and C1-C6 alkoxy;
Y 1 、Y 2 、Z 1 、Z 2 the same or different, each independently selected from hydrogen, C1-C20 alkyl and C1-C20 alkoxy;
X 1 、X 2 identical or different, each independently selected from a five-or six-membered ring containing carbon or carbon and nitrogen, optionally substituted with a substituent selected from cyano, nitro, halogen, C1-C6 alkyl and C1-C6 alkoxy;
q is a bond-free or a single chemical bond;
in the formula (II), R 1 、R 2 And R is 3 The same or different, each independently selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C3-C20 cycloalkenyl, and C6-C36 aryl, optionally, the C1-C20 alkyl, C3-C20 cycloalkyl, C3-C20 cycloalkenyl, and C6-C36 aryl may be substituted with substituents selected from the group consisting of cyano, nitro, halogen, C1-C6 alkyl, and C1-C6 alkoxy.
According to a preferred embodiment of the invention, in formula (I), X is selected from the group consisting of 1,1 '-biphenyl-2, 2' -diyl, 3 '-bis-tert-butyl-5, 5' -dimethoxy-1, 1 '-biphenyl-2, 2' -diyl, 3', 5' -tetra-tert-butyl-1, 1 '-biphenyl-2, 2' -diyl, 1.4-phenylene, 1, 3-phenylene, 1, 5-naphthylene and 2,7,9,9-tetramethyl-9H- (clamp) xanthene-4, 5-diyl.
According to a preferred embodiment of the invention, in formula (I), Y 1 、Y 2 、Z 1 、Z 2 The same or different are each independently selected from hydrogen, C1-C10 alkyl and C1-C10 alkoxy.
According to a preferred embodiment of the invention, in formula (I), Y 1 、Y 2 、Z 1 、Z 2 The same or different are each independently selected from hydrogen, C1-C6 alkyl and C1-C6 alkoxy.
According to a preferred embodiment of the invention, in formula (I), Y 1 、Y 2 、Z 1 、Z 2 The same or different are each independently selected from hydrogen, tert-butyl and methoxy.
According to a preferred embodiment of the invention, in formula (I), X 1 、X 2 The same or different, each independently selected from a six-membered ring containing carbon and a five-membered ring containing carbon and nitrogen.
According to a preferred embodiment of the invention, in formula (II), R 1 、R 2 And R is 3 The same or different, each independently selected from C1-C10 alkyl, C3-C20 cycloalkyl and C6-C15 aryl.
In the present invention, ligand I is a bisphosphite ligand and ligand II is a monodentate phosphine ligand.
According to some embodiments of the invention, the exemplary compounds of ligand I include:
according to some embodiments of the invention, the synthesis of ligand I bisphosphite ligand comprises two types of reactions, one is an oxidative coupling reaction of phenol, biphenol is made from substituted monophenols, and the other is a reaction of P-Cl with removal of HCl by HO-R.
According to some embodiments of the present invention, the rhodium catalyst precursor is selected from at least one of a halogen compound, a carbonyl compound, and an acetylacetonate dicarbonyl compound, and the rhodium catalyst precursor is not limited to the above-mentioned compounds.
According to some preferred embodiments of the invention, the rhodium catalyst precursor is selected from at least one of rhodium tris (triphenylphosphine) carbonyl hydride, rhodium tris (triphenylphosphine) chloride, and rhodium acetylacetonate dicarbonyl.
According to some embodiments of the invention, the rhodium catalyst precursor is rhodium acetylacetonate dicarbonyl and/or rhodium tris (triphenylphosphine) carbonyl hydride.
According to some embodiments of the invention, the molar ratio of ligand to rhodium catalyst precursor is (1-200): 1.
according to some embodiments of the invention, the molar ratio of ligand I to ligand II is (1-20): 1.
in a second aspect, the present invention provides the use of a catalyst composition according to the first aspect for the preparation of higher aldehydes.
According to some embodiments of the invention, the higher aldehydes have the general formula RCHO, wherein R is a C5-C20 alkyl group.
In a third aspect, the present invention provides a process for the preparation of higher aldehydes comprising reacting a higher number olefin, carbon monoxide and hydrogen in an organic solvent system comprising the catalyst composition of the first aspect to produce higher aldehydes.
According to some embodiments of the invention, the higher aldehydes have the general formula RCHO, wherein R is a C5-C20 alkyl group.
According to some embodiments of the invention, the catalyst composition comprises a rhodium catalyst precursor and a ligand, the ligand being a ligand I of formula (I) and/or a ligand II of formula (II),
in formula (I), X is selected from the group consisting of C6-C28 organic divalent bridging arylene, optionally substituted with substituents selected from the group consisting of cyano, nitro, halogen, C1-C6 alkyl, and C1-C6 alkoxy;
Y 1 、Y 2 、Z 1 、Z 2 the same or different, each independently selected from hydrogen, C1-C20 alkyl and C1-C20 alkoxy;
X 1 、X 2 identical or different, each independently selected from a five-or six-membered ring containing carbon or carbon and nitrogen, optionally substituted with a substituent selected from cyano, nitro, halogen, C1-C6 alkyl and C1-C6 alkoxy;
q is a bond-free or a single chemical bond;
in the formula (II), R 1 、R 2 And R is 3 The same or different, each independently selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C3-C20 cycloalkenyl, and C6-C36 aryl, optionally, the C1-C20 alkyl, C3-C20 cycloalkyl, C3-C20 cycloalkenyl, and C6-C36 aryl may be substituted with substituents selected from the group consisting of cyano, nitro, halogen, C1-C6 alkyl, and C1-C6 alkoxy.
According to a preferred embodiment of the invention, in formula (I), X is selected from the group consisting of 1,1 '-biphenyl-2, 2' -diyl, 3 '-bis-tert-butyl-5, 5' -dimethoxy-1, 1 '-biphenyl-2, 2' -diyl, 3', 5' -tetra-tert-butyl-1, 1 '-biphenyl-2, 2' -diyl, 1.4-phenylene, 1, 3-phenylene, 1, 5-naphthylene and 2,7,9,9-tetramethyl-9H- (clamp) xanthene-4, 5-diyl.
According to a preferred embodiment of the invention, in formula (I), Y 1 、Y 2 、Z 1 、Z 2 The same or different, each independently selected from hydrogen, C1-C10Alkyl and C1-C10 alkoxy.
According to a preferred embodiment of the invention, in formula (I), Y 1 、Y 2 、Z 1 、Z 2 The same or different are each independently selected from hydrogen, C1-C6 alkyl and C1-C6 alkoxy.
According to a preferred embodiment of the invention, in formula (I), Y 1 、Y 2 、Z 1 、Z 2 The same or different are each independently selected from hydrogen, tert-butyl and methoxy.
According to a preferred embodiment of the invention, in formula (I), X 1 、X 2 The same or different, each independently selected from a six-membered ring containing carbon and a five-membered ring containing carbon and nitrogen.
According to a preferred embodiment of the invention, in formula (II), R 1 、R 2 And R is 3 The same or different, each independently selected from C1-C10 alkyl, C3-C20 cycloalkyl and C6-C15 aryl.
In the present invention, ligand I is a bisphosphite ligand and ligand II is a monodentate phosphine ligand.
According to some embodiments of the invention, the exemplary compounds of ligand I include:
according to some embodiments of the invention, the synthesis of ligand I bisphosphite ligand comprises two types of reactions, one is an oxidative coupling reaction of phenol, biphenol is made from substituted monophenols, and the other is a reaction of P-Cl with removal of HCl by HO-R.
According to some embodiments of the present invention, when the catalyst composition of the present invention comprising ligand M is used in the hydroformylation of high olefins, the catalyst is more effective, the conversion of olefins is higher, the selectivity of linear high aldehydes is higher, and the isomerization of olefins is significantly reduced.
According to some embodiments of the present invention, the rhodium catalyst precursor is selected from at least one of a halogen compound, a carbonyl compound, and an acetylacetonate dicarbonyl compound, and the rhodium catalyst precursor is not limited to the above-mentioned compounds.
According to some preferred embodiments of the invention, the rhodium catalyst precursor is selected from at least one of rhodium tris (triphenylphosphine) carbonyl hydride, rhodium tris (triphenylphosphine) chloride, and rhodium acetylacetonate dicarbonyl.
According to some embodiments of the invention, the rhodium catalyst precursor is rhodium acetylacetonate dicarbonyl and/or rhodium tris (triphenylphosphine) carbonyl hydride.
According to some embodiments of the invention, the molar ratio of ligand to rhodium catalyst precursor is (1-200): 1.
according to some embodiments of the invention, the molar ratio of ligand I to ligand II is (1-20): 1.
according to some embodiments of the invention, the high carbon number olefin has a structure as shown in formula (III),
wherein R4 and R5 are selected from hydrogen, C1-C20 alkyl or C6-C20 aryl, optionally substituted with 0 to 5 substituents selected from nitro, halogen or C1-C6 alkyl.
According to a preferred embodiment of the invention, in formula (III), the substituents are selected from nitro, fluoro, chloro, bromo, methyl, ethyl, propyl or butyl.
According to some embodiments of the invention, the high carbon number olefin refers to an olefin of six carbons or more.
The rhodium/monodentate phosphine ligand, rhodium/bisphosphite ligand and monodentate phosphine ligand catalyst composition is prepared by dissolving a rhodium catalyst precursor, bisphosphite ligand and monodentate phosphine ligand in one or more solvents in advance, wherein the solvents are solvents capable of better dissolving high-carbon-number olefins, rhodium catalyst precursors, bisphosphite ligands and monodentate phosphine ligands.
According to some embodiments of the invention, the organic solvent system comprises one or more of alkanes, substituted alkanes, benzene substituents, and aldehydes.
According to a preferred embodiment of the present invention, the organic solvent system is selected from at least one of toluene, xylene, nonanal and decane.
According to some embodiments of the invention, the molar ratio of the catalyst composition to the higher carbon number olefin is from 1:2000 to 1:10000, based on the molar ratio of rhodium precursor compound to the higher carbon number olefin in the catalyst composition.
According to some embodiments of the invention, the molar ratio of hydrogen to carbon monoxide is from 1:1 to 4:1.
According to some embodiments of the invention, the concentration of rhodium catalyst precursor in the catalyst composition is in the range of 0.01-5mmol/L.
According to some embodiments of the invention, the temperature of the reaction is 50-150 ℃.
According to a preferred embodiment of the invention, the temperature of the reaction is 60-120 ℃.
According to some embodiments of the invention, the reaction time is 0.5-3 hours.
According to a preferred embodiment of the invention, the reaction time is 1-2 hours.
According to some embodiments of the invention, the pressure of the reaction is 0.5-3MPa.
According to a preferred embodiment of the invention, the pressure of the reaction is between 0.5 and 1.5Mpa.
The inventors of the present invention found in the course of the study that in the hydroformylation of high-carbon olefins, when rhodium/monodentate phosphine ligand was used as a catalyst, the conversion of olefins and the selectivity of linear high-carbon aldehydes were both low, and no isomerization of olefins was observed. In the hydroformylation reaction of the high-carbon olefin, when rhodium/bisphosphite ligand is used as a catalyst, the olefin is completely converted, the selectivity of linear high-carbon aldehyde is higher, and the isomerization of the olefin is serious. In the hydroformylation reaction of the high-carbon olefin, when rhodium/bisphosphite ligand and monodentate phosphine ligand combination are used as catalysts, the olefin is completely converted, the selectivity of linear high-carbon aldehyde is obviously improved, and the isomerization of the olefin is obviously reduced. Presumably, this is because the monodentate phosphine ligand coordinates to rhodium to stabilize the active species and reduce the ability of rhodium to accept electrons.
Detailed Description
The present invention will be further illustrated by the following specific examples, but it should be understood that the scope of the present invention is not limited thereto.
Example 1
The synthesis method of the ligand M comprises the following steps: 50g of sodium hydroxide, 2g of sodium dodecyl sulfate, 250ml of distilled water and 100g of 2, 4-di-tert-butylphenol are respectively added into a three-mouth bottle, the temperature is slowly raised to 80 ℃, 30% of hydrogen peroxide is dripped, the temperature is maintained at 80-90 ℃, the reaction is carried out for 2 hours, the cooling is carried out to room temperature, the filtration and the recrystallization are carried out, and the intermediate A with the melting point of 200-203 ℃ is obtained. Under the protection of nitrogen, adding 120ml of newly distilled phosphorus trichloride into 60g of 2,2' -biphenol, heating and refluxing for 2 hours, decompressing and distilling out excessive phosphorus trichloride to obtain an intermediate B, and adding 90ml of tetrahydrofuran to obtain a tetrahydrofuran solution of the intermediate B. At 50 ℃, adding a tetrahydrofuran solution of an intermediate A with the concentration of 0.55g/ml into a tetrahydrofuran solution of an intermediate B in a dropwise manner, stirring for reacting for 2 hours, cooling to room temperature, filtering to remove generated pyridine hydrochloride, evaporating a solvent from a filtrate, washing with acetonitrile, and filtering to obtain a white ligand M with the melting point of 150-152 ℃.
Example 2
A toluene solution in which 50mmol/L triphenylphosphine and 0.55mmol/L rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100ml autoclave equipped with stirring, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:1), keeping the pressure in the kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle by using an ice water bath. The reaction solution was checked by gas chromatography, the 1-octene conversion was 67%, the nonanal yield was 67%, and the normal aldehyde/iso aldehyde (normal-iso ratio) was 4.3.
Example 3
A toluene solution in which 4.5mmol/L of ligand M and 1mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100ml autoclave equipped with stirring, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:1), keeping the pressure in the kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle by using an ice water bath. The reaction liquid is detected by gas chromatography, the 1-octene conversion rate is 98%, a large amount of cis-octene and trans-2-octene are present in the product, the nonanal yield is 33%, and the normal-to-iso ratio is 26.8.
Example 4
A toluene solution in which 4.5mmol/L of ligand L and 1mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100ml autoclave equipped with stirring, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:1), keeping the pressure in the kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle by using an ice water bath. The reaction liquid is detected by gas chromatography, the conversion rate of 1-octene is 98%, a large amount of cis-trans-2-octene exists in the product, the yield of nonanal is 4.4%, and the normal-to-iso ratio is 25.
Example 5
A toluene solution in which 4.5mmol/L of ligand M, 10mmol/L of triphenylphosphine and 0.55mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100ml autoclave equipped with stirring, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:1), keeping the pressure in the kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle by using an ice water bath. The reaction liquid is detected by gas chromatography, the conversion rate of 1-octene is 75%, the cis-trans 2-octene content in the product is obviously reduced, the nonanal yield is 50%, and the normal-to-iso ratio is 81.
Example 6
A toluene solution containing 10mmol/L of ligand M, 10mmol/L of triphenylphosphine and 1mmol/L of rhodium acetylacetonate dicarbonyl was charged into a stirred 100ml autoclave, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:1), keeping the pressure in the kettle constant at 1MPa, reacting for 6 hours, stopping the reaction, and cooling the reaction kettle by using an ice water bath. The reaction liquid is detected by gas chromatography, 1-octene is completely converted, the yield of nonanal is 91%, and the normal-to-iso ratio is 79.
Example 7
A toluene solution containing 5mmol/L of ligand M, 50mmol/L of triphenylphosphine and 3mmol/L of rhodium acetylacetonate dicarbonyl was charged into a stirred 100ml autoclave, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 60 ℃, introducing synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:1), keeping the pressure in the kettle constant at 1MPa, reacting for 1.5 hours, stopping the reaction, and cooling the reaction kettle by using an ice water bath. The reaction liquid is detected by gas chromatography, the conversion rate of 1-octene is 95%, the temperature is reduced, the amount of cis-trans-2-octene in the product is increased, the yield of nonanal is 70%, and the normal-to-iso ratio is 84.
Example 8
A toluene solution in which 4.5mmol/L of ligand M, 50mmol/L of triphenylphosphine and 0.55mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100ml autoclave equipped with stirring, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 120 ℃, introducing synthesis gas, keeping the pressure in the reactor constant at 1MPa, reacting for 6 hours, stopping the reaction, and cooling the reaction kettle by using ice water bath. The reaction liquid is detected by gas chromatography, the 1-octene is completely converted, the temperature is raised, the amount of cis-octene and trans-octene in the product is reduced, the nonanal yield is 95%, and the normal-to-iso ratio is 73.
Example 9
A toluene solution in which 6mmol/L of ligand M, 30mmol/L of triphenylphosphine and 1mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a stirred 100ml autoclave, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the reactor constant at 0.5MPa, reacting for 6 hours, stopping the reaction, and cooling the reaction kettle by using ice water bath. The reaction liquid is detected by gas chromatography, the 1-octene is completely converted, the pressure is reduced, the amount of cis-octene and trans-octene in the product is increased, the nonanal yield is 89%, and the normal-to-iso ratio is 72.
Example 10
A toluene solution in which 4.5mmol/L of ligand M, 4.5mmol/L of triphenylphosphine and 3mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100ml autoclave equipped with stirring, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the reactor constant at 3MPa, reacting for 6 hours, stopping the reaction, and cooling the reaction kettle by using ice water bath. The reaction liquid is detected by gas chromatography, the 1-octene is completely converted, the pressure is increased, the amount of cis-octene and trans-octene in the product is increased, the nonanal yield is 50%, and the normal-to-iso ratio is 20.
Example 11
A toluene solution containing 4.5mmol/L of ligand M and 0.55mmol/L of rhodium acetylacetonate dicarbonyl was charged into a stirred 100ml autoclave, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the reactor constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle by using ice water bath. The reaction liquid is detected by gas chromatography, the conversion rate of 1-octene is 98%, the cis-trans 2-octene content in the product is larger, the nonanal yield is 35%, and the normal-to-iso ratio is 26.
Example 12
A toluene solution in which 10mmol/L triphenylphosphine and 0.55mmol/L rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100ml autoclave equipped with stirring, and the mixture was stirred and complexed for several minutes. 14g of 1-octene was added to the kettle. The air in the kettle was replaced 6 times with synthesis gas. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the reactor constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle by using ice water bath. The reaction liquid is detected by gas chromatography, the 1-octene conversion rate is 30%, the nonanal yield is 30%, and the normal-to-iso ratio is 4.
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (13)
1. A process for the preparation of a higher aldehyde comprising reacting a higher olefin, carbon monoxide and hydrogen in an organic solvent system comprising a catalyst composition comprising a rhodium catalyst precursor and a ligand of formula I of formula (I) and a ligand of formula II of formula (II) to produce a higher aldehyde of formula RCHO wherein R is a C9-C20 alkyl group,
in the formula (I), X is selected from 1,1 '-biphenyl-2, 2' -diyl, 3 '-di-tert-butyl-5, 5' -dimethoxy-1, 1 '-biphenyl-2, 2' -diyl, 3', 5' -tetra-tert-butyl-1, 1 '-biphenyl-2, 2' -diyl;
Y 1 、Y 2 、Z 1 、Z 2 the same or different, each independently selected from hydrogen, C1-C20 alkyl and C1-C20 alkoxy;
X 1 、X 2 identical or different, each independently selected from six-membered rings containing carbon;
q is a bond-free or a single chemical bond;
in the formula (II), R 1 、R 2 And R is 3 Identical or different, each independently selected from C1-C10 alkyl, C3-C20 cycloalkyl and C6-C15 aryl;
the rhodium catalyst precursor is selected from a halogen compound, a carbonyl compound or an acetylacetonate dicarbonyl compound of rhodium;
the molar ratio of ligand to rhodium catalyst precursor is (18.3-200): 1, a step of; the temperature of the reaction is 60-120 ℃, the pressure of the reaction is 0.5-1.5Mpa, and the molar ratio of the ligand I to the ligand II is (1-20): 1.
2. the method of claim 1, wherein Y 1 、Y 2 、Z 1 、Z 2 Each independently selected from hydrogen, C1-C10 alkyl, and C1-C10 alkoxy;
and/or the six-membered ring containing carbon is substituted with a substituent selected from cyano, nitro, halogen, C1-C6 alkyl and C1-C6 alkoxy.
3. The method of claim 1, wherein Y 1 、Y 2 、Z 1 、Z 2 Each independently selected from the group consisting of hydrogen, C1-C6 alkyl, and C1-C6 alkoxy.
4. The method of claim 1, wherein Y 1 、Y 2 、Z 1 、Z 2 Each independently selected from the group consisting of hydrogen, t-butyl, and methoxy.
5. The production method according to claim 1, wherein the rhodium catalyst precursor is selected from at least one of tris (triphenylphosphine) rhodium carbonyl hydride, tris (triphenylphosphine) rhodium chloride, and rhodium acetylacetonate dicarbonyl.
6. The process according to claim 1, wherein the rhodium catalyst is rhodium acetylacetonate dicarbonyl and/or rhodium tris (triphenylphosphine) carbonyl hydride.
7. The preparation method according to claim 1, wherein the high-carbon-number olefin has a structure represented by formula (III),
wherein R is 4 And R is 5 Selected from hydrogen, C1-C20 alkyl or C6-C20 aryl, optionally substituted with 0 to 5 substituents selected from nitro, halogen or C1-C6 alkyl.
8. The method of claim 7, wherein the substituents are selected from nitro, fluoro, chloro, bromo, methyl, ethyl, propyl, and butyl.
9. The method of any one of claims 1-8, wherein the organic solvent system comprises one or more of alkanes, substituted alkanes, benzene substituents, and aldehydes.
10. The production method according to claim 9, wherein the organic solvent is at least one selected from toluene, xylene, nonanal and decane.
11. The production method according to any one of claims 1 to 8, wherein the molar ratio of the catalyst composition to the higher carbon number olefin is 1:2000 to 1:10000 in terms of the molar ratio of the rhodium precursor compound in the catalyst composition to the higher carbon number olefin; and/or the molar ratio of the hydrogen to the carbon monoxide is 1:1-4:1; and/or the concentration of rhodium catalyst precursor in the catalyst composition is in the range of 0.01-5mmol/L.
12. The method according to any one of claims 1 to 8, wherein the reaction time is 0.5 to 3 hours.
13. The method of claim 12, wherein the reaction time is 1-2 hours.
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